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It is probably sufficient that the rate limiting ρ = disintegration rate or hydrolysis rate of solid
degradation step is modeled utilizing the proper substrate (kg COD solid substrate m-3 d-1 where COD =
temperature effect(s). It is however not always obvious chemical oxygen demand), Xdis,hyd = solid substrate
what the rate-limiting step is. Hydrolysis and concentration (kg COD solid substrate m-3), Kdis,hyd =
disintegration are often assumed rate limiting for temperature dependent kinetic parameter for
particle rich substrates, such as manure, but this may be disintegration or hydrolysis (d-1). Disintegration is
altered by pre-treatment. Particle rich manure filtrate, typically considered the rate-limiting step for substrates
for which the rate-limiting step is unknown, is used as containing mainly particles, while hydrolysis of
feed in this study. proteins, lipids and carbohydrates is the rate limiting in
Modelling AD at thermophilic (45 - 70 °C) and high rate digesters and then only disintegration of
psychrophilic (4 - 15 °C) temperatures with possible decaying microorganisms is accounted for (Batstone et
other degradation paths (Vavilin et al., 1997) is not al., 2002).
attempted here. Temperature effects on diffusion are
assumed insignificant in the range investigated.
An intention is that the model can be used to reveal
optimal sludge bed AD temperatures, such as to
investigate the potential for reducing heating
requirements by reactor operation at temperatures below
35°C.
The purpose of this study is to quantify temperature
effects on AD modelling by establishing and testing an
extended ADM1 (“ADM1-T”) to account for
temperature effects on model parameters.
The model is tested on data from a 220 liter AD
sludge bed reactor treating diary manure filtrate for 4
months of varying loads and with step temperature
changes between 25, 30 and 35 °C.
Additional aims are:
(1) Distinguish between physical and biological
Figure 1. COD flow diagram of the Anaerobic Digestion
effects of temperature;
Model No.1 (Adapted from Batstone et al., 2002)
(2) Evaluate temperature effects in sludge bed AD
showing the biochemical reactions for which temperature
and
effects have been included as arrows.
(3) Look for limiting reaction steps for process
capacity by testing and modeling AD at different loads
and temperatures. Each intracellular enzyme mediated biochemical
This should improve our general understanding of reaction (acidogenesis, acetogenesis, methanogenesis)
how, where and when temperature influences AD (Fig. 1) is generally approximated by a Monod type
processes. saturation function where the reaction rate of substrate
uptake by organism, ρ (kg COD substrate m-3 d-1), can
2 Materials and Methods be described as:
Temperature dependent kinetic parameters for both
biochemical and physico-chemical processes are ρ=� ∙X∙ +�
∙I (3)
retrieved from literature survey. Other relevant model
parameters are retrieved from batch tests and compared Equation (3) contains the maximum substrate uptake
against continuous AD using diary manure filtrate. rate constant km (kg COD substrate kg COD biomass-1
d-1), X = biomass concentration (kg COD biomass m-3),
2.1 Model Parameters S = substrate concentration (kg COD substrate m-3), KS
2.1.1 Biochemical kinetic parameters = half saturation constant (kg COD substrate m-3) and I
= inhibition factor. The growth of biomass, X, is
Kinetic temperature dependent parameters for expressed through the yield, Y (kg COD biomass X kg-
biochemical processes in ADM1-T are Kdis, Khyd, km, 1
COD substrate) of uptake of substrate, while biomass
Kd, Y and KS, which are recommended in ADM1 for 35 death is described by Kd (d-1) (Table 1).
°C and used as a reference (Table 1). Kdis and Khyd are Temperature effects on Khyd and km are retrieved
for 1.st order extracellular reactions disintegration and from literature sources. The hydrolysis kinetic
hydrolysis (2). parameter is also tested by a set of laboratory
experiments to find both the khyd for this substrate and
� = ��� ∙ ��� (2) the effect of low temperature. A Hinshelwood double
,ℎ�� ,ℎ��
Arrhenius function is recommended (Batstone et al., degraders at 10 – 40 °C. Calculated relative factors from
2002) as the temperature dependency for the these temperature effects are also in Table 3. Reactions
biochemical reactions expressed through km. The that were not found were estimated by using factors
affinity for the substrate parameter KS is therefore not from “nearby” reactions in Fig. 1: The same temperature
altered. Monod (1949) assumes a saturation relationship effect as for sugar uptake is used on amino acids and
between substrate concentration and growth rate while fatty acids uptake. The same temperature effect for
growth yield remained constant over a wide range of hydrogen uptake as for acetate uptake is also used.
substrate concentrations that requires a constant KS. We
extend this assumption to temperature and evaluate if
temperature effects on yield can be ignored. The death Table 3. Relative change of the kinetic parameters Kdis,
Khyd and km with temperature. Calculated from reported
of biomass Kd has a constant small value in ADM1. The
data in (A) Donoso-Bravo et al. (2009), and (B) Rebac et
temperature effect, if any, is assumed small and not
al. (1995).
altered.
Process Temperature (°C) Ref.
25 30 35
Table 1 Biochemical processes temperature dependent Disintegration, Same as for hydrolysis
kinetic parameters. Kdis of carbohydrates
Parameter Biochemical Expre Denomination Hydrolysis of 0.48 0.74 1.00 A
ssion carbohydrates,
Kdis disintegration 2 d-1 Khyd, su
Khyd hydrolysis 2 d-1 Hydrolysis of Same as for hydrolysis
km max substrate 3 kg COD protein, Khyd, pr of carbohydrates
uptake rate substrate Hydrolysis of lipids, Same as for hydrolysis
constant m-3 d-1 Khyd, li of carbohydrates
KS half saturation 3 kg COD Sugar 0.21 0.22 1.00
constant substrate m-3 A
Uptake, km
Y biomass kg COD Amino acid uptake, Same as for sugar
growth yield biomass km uptake
kg-1 COD Same as for sugar
substrate Fatty acid uptake, km
uptake
Kd death rate of d-1 Butyrate uptake, km 0.67 0.86 1.00 B
biomass Propionate uptake 0.70 0.90 1.00 B
Aceticlastic 0.69 0.93 1.00
A
Relative factors of the relevant temperatures, 35, 30 methanogens, km
and 25 °C are calculated from reported temperature Aceticlastic 0.48 0.70 1.00
B
effect (Henze and Harremoës, 1983) on the overall methanogens, km
biogas production (Table 2). These factors are applied Hydrogenotroph Same as for aceticlastic
for all the kinetic parameters Kdis, Khyd and km for all the methanogens, km methanogens
degradation steps since the limiting reaction is unknown
as a first approach. Three different simulations were done;
H: using the same temperature effect (Table 2) for all
Table 2. Relative temperature factors for kinetic the degradation steps.
parameters for the overall biogas production. Calculated D: using all the temperature effects from Table 3 but
from Henze and Harremoës (1983). with methanogenesis from Donoso-Bravo et al. (2009)
Temperature (°C) 25 30 35
R: using all the temperature effects from Table 3 but
Temperature factor 0.42 0.87 1 with methanogenesis from Rebac et al. (1995)
2.1.2 Physio-chemical parameters
Temperature effects on the kinetic parameters that are
different for each degradation equation are also The temperature dependencies of the temperature
implemented. Relative temperature effects for dependent kinetic parameters ka and kH (Table 4) are in
hydrolysis, acidogenesis and acidoclastic the standard ADM1 while the temperature dependency
methanogenesis of respectively starch, glucose and of the mass transfer coefficient kLa is implemented here.
acetic acid through batch tests at 15-45 °C (Donoso- Physico-chemical equilibrium is modeled based on
Bravo et al., 2009) is used to calculate temperature the law of mass action for aqueous substances and on
factors for each reaction (Table 3). Relative temperature Henry’s law to model the solubility of a gas in water.
effects on individual reactions are also reported by Both are temperature dependent; which are given by
Rebac et al. (1995) for butyrate, propionate and acetate equations (4) and (5) respectively.
Accumulated biogas
2.3.2 Monitoring and analysis 200
A comprehensive online- and offline-testing scheme 150
was used to monitor the AD reactor. Biogas production 100
(mL)
(L d-1), gas composition (fractions of CO2 and CH4), 50
liquid flow and reactor temperature were monitored 0
continuously online as described by Haugen et al. 0 50 100 150
(2013). Substrate and effluent samples were collected 1- Time (d)
2 times a week. Total chemical oxygen demand (CODT),
soluble COD (CODS), total solids (TS), volatile solids B
(VS), total suspended solids (TSS), volatile suspended Accumulated biogas 250
solids (VSS), pH, alkalinity, NH4+-N and VFA's 200
(acetate, propionate, butyrate, iso-butyrate, valerate, 150
iso-valerate) were analyzed as described in Bergland et 100
(mL)
al. (2015). 50
0
3 Results 0 50 100 150
3.1 Biodegradability and hydrolysis input to the Time (d)
model
Figure 3. Batch test data and fitted line for 35 °C (A) and
The batch tests gave a total biodegradable fraction of 23 °C (B) used to calculate khyd.
0.26 of the CODT. The non-degradable is therefore 74
% for the manure substrate COD used. The fractions of
protein, carbohydrates and lipids in the biodegradable The average hydrolysis factor for sludge is khyd =
fraction are set to 0.27 (f_pr), 0.51 (f_ch) and 0.22 (f_li) 0.183 at 35 °C (Batstone et al., 2002). The khyd values
respectively (Table 6) as found for slurry cattle manure for cow manure used here are therefor changed by
(Møller et al., 2003). Tests of the temperature multiplying the various coefficients for sludge with the
dependency revealed that 96 % ± 2 % of the biogas factor 0.13/0.183 at 35 °C to: khyd_ch = 0.18 from 0.25 d-
1
production at 35 °C were achieved at 23 °C in the batch , khyd_li to 0.07 from 0.1 and khyd_pr to 0.14 from 0.2 d-1
tests, confirming that yields are quite insensitive to for all the simulations. The khyd values are similarly
temperature. The effect is implemented as 96 % at 25 adjusted down for the lower temperatures with relative
°C and 98 % at 30 °C. The fraction of biodegradable factors of 1 at 35 °C, 0.74 at 30 °C and 0.47 at 25 °C
from particles is below 0.38 and the rest from soluble which is almost identical to the temperature effect found
organics, determined based on the COD contents before by Donoso-Bravo et al. (2009) for carbohydrates (Table
and after the batch test (Table 5). 0.3 is used as 3).
biodegradable fraction from particles and 0.7 from The batch results (Fig. 3) also confirms that
dissolved COD in the model. temperature influence AD kinetics much more than
stoichiometry (khyd is reduced by 60 % while yield by 4
% at 23 °C compared to at 35 °C).
Table 5. Diary manure filtrate parameters used to
calculate the COD content of the degradable and non- 3.2 AD sludge bed reactor data input to the
degradable fractions of particulates and dissolved model
organics of the AD reactor substrate.
Property Before After Δ COD The biogas production and effluent concentrations of the
CODT 50 37 13 pilot AD are presented with the simulated results in
CODS 14 6 8 Figure 5 - 6 during the given load and temperature step
CODT - CODS = 36 31 changes (Fig. 4). Some scattering in measured AD
CODparticles substrate composition may be due to real, uncontrolled,
fluctuations in the influent with seasonal and other
changes in farm operation. Sampling and measurement and thereby establish model steady state conditions that
errors are also likely on particle rich manure samples. correspond to that observed at what is defined as time
Such fluctuations are reduced through the AD reactor, zero in this study (Fig. 5 and 6). The CO2 concentration
as expected. The inlet fluctuations are considered noise, in the biogas was adjusted by adding a constant inflow
so the inflow concentrations are therefore smoothened substrate HCO3 level (Table 6). The modeled effluent
by median values, floating by the amount of samples pH level was forced to match measured values by
indicated after each property, for NH4-N (20), CODT adjusting the addition of a constant concentration of ions
(6), CODS (4), acetate (20), propionate (20) and butyrate in the inflow substrate. The active reactor biomass
(20). concentrations were also tuned to match steady state
performance, found to add up to a level below 10 g COD
L-1 reactor. This is well below the upper limit of 40 g
Table 6. Substrate inflow content to the AD reactor in the COD L-1 reactor for sludge bed AD (Kleerebezem et al.,
simulation.
2006).
Para Content Formula Denominat
40
meter ion
Temperature (°C)
35
X_c composite 0 g COD L-1
30
X_pr protein f_pr*0.11* g COD L-1 25
(CODT - CODS) 20
X_li lipid f_li*0.11* g COD L-1 0 50 100 150
(CODT - CODS) Time (d)
X_ch carbo- f_ch*0.11* g COD L-1
hydrates (CODT - CODS) 0,04
Load (m3 d-1)
-1
X_I solid inert 0.86* g COD L 0,03
(CODT - CODS) 0,02
S_I soluble 0.03* g COD L-1 0,01
inert (from (CODT - CODS) 0
solid) 0 50 100 150
-1
CODT total 50.6 ± 2 g COD L Time (d)
methanogenesis can be especially sensitive to load day gives reasonable fit (Fig. 6). Larger model
transitions and SRT. numerical step size overestimates this initial peak. The
SRT is calculated using tres_x = 15, since it gave the experimental temperature steps lasted for 0.4 and 0.5
best correlations, for the remaining simulations to days from 25 to 30 °C and 30 to 35 °C, respectively.
evaluate the impact of the various temperature corrected The three simulations “H”, “D” and “R” gave the
kinetic constants. A lower tres_x, implying lower SRT same biogas production except for “H” at 30 °C which
than that proposed by Batstone et al. (2002) seem coincidence with the original ADM1 model. The
reasonable for the present case since HRT was higher original model gave higher biogas production at both 25
than typical for sludge bed AD. °C and 30 °C but similar to the others at 35 °C as
expected (Fig. 6).
A tres_x 6 tres_x 10
A
tres_x 15 tres_x 20
0,3
0,2
0,25
0,2 0,15
0,15 0,1
0,1 0,05
0,05 0
0 0 50 100 150
0 50 100 150 Time (d)
Time (d)
B
2
B
Acetate concentration
1,5
3,5
(g COD L-1)
Acetate concentration
3
2,5 1
2
(g COD L-1)
1,5 0,5
1
0,5
0 0
0 50 100 150 0 50 100 150
0,2
0,15
3.3.2 Temperature effects 0,1
0,05
The simulated biogas production and effluent
concentrations (Fig. 6) for the various temperature 0
models shows good fit to the measured values. The 0 50 100 150
various temperature effect parameters (Donoso-Bravo et Time (d)
al., 2009; Rebac et al., 1995; Henze and Harremoës,
1983) differ most in simulating acetate concentrations, Figure 6. Biogas production rate (A) and effluent acetic
but less on the overall biogas production rate. (B) and propionic (C) concentration values temperature
The simulated transient peaks in biogas production dependency using original model, Rebac et al. (1995),
following temperature increases are in the same range as Donoso-Bravo et al. (2009), Henze and Harremoës (1983)
observed (Fig 6). Peak shape depends, however, on with tres_x = 15 d. Experimental (♦) and simulated
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